KR20040087888A - Coating composition for insulating film production, preparation method of insulation film by using the same, insulation film for semi-conductor device prepared therefrom, and semi-conductor device comprising the same - Google Patents

Abstract

PURPOSE: Provided are a coating composition for forming an insulating membrane having a low dielectric property and an improved mechanical property(modulus), a process for producing the low dielectric insulating membrane by using the coating composition, and a semiconductor element containing the insulating membrane, which improve dielectric characteristic and physical properties by comprising low molecular weight organopolysiloxane prepolymer and water. CONSTITUTION: The coating composition for the insulating membrane contains 100pts.wt. of an organopolysiloxane prepolymer having a weight average molecular weight of 500-30000, 200-2000pts.wt. of an organic solvent, and 5-60pts.wt. of water, wherein the molar ratio of hydroxy groups to the total functional groups capable of a condensation reaction in the organopolysiloxane prepolymer is more than 80%. The low dielectric insulating membrane is produced by a process comprising the steps of: preparing the coating composition for the insulating membrane; spreading the coating composition on a substrate of a semiconductor element; drying and calcining the coating composition. And the semiconductor element contains the low dielectric insulating membrane.

Description

Coating composition for forming an insulating film, a method of manufacturing a low dielectric insulating film using the same, and a low dielectric insulating film for a semiconductor device manufactured therefrom and a semiconductor device comprising the same TECHNICAL FIELD, PREPARATION METHOD OF INSULATION FILM BY USING THE SAME, INSULATION FILM FOR SEMI-CONDUCTOR DEVICE PREPARED THEREFROM, AND SEMI-CONDUCTOR DEVICE COMPRISING THE SAME}

The present invention relates to a coating composition for forming an insulating film, a method of manufacturing a low dielectric insulating film using the same, and a low dielectric insulating film for a semiconductor device manufactured therefrom, and a semiconductor device including the same. More specifically, the dielectric constant is low and the mechanical strength is low. A coating composition for forming an insulating film capable of forming an insulating film having excellent elastic modulus, a method for manufacturing a low dielectric insulating film using the same, and a low dielectric insulating film for a semiconductor device manufactured therefrom and a semiconductor device comprising the same.

In recent years, as the degree of integration of semiconductor devices has increased, the wiring density has increased, and the spacing of metal wirings has gradually decreased. As a result, parasitic capacitance between metal wires increases, resulting in a problem that device characteristics cannot be expected using an existing insulating film due to RC delay, cross-talk between metals, and increased power consumption. Introduction of low dielectric materials is essential to the wiring process.

In the conventional interlayer insulating materials of semiconductor devices such as IC and LSI, SiO ₂ having a dielectric constant of 4.0 is mostly used, and a low dielectric material is fluorine-doped silicate (F-SiO ₂ ) applied to some devices. However, in the case of F-SiO ₂ , as the fluorine content increases, it becomes a thermally unstable state, which makes it difficult to lower the dielectric constant below 3.5. Accordingly, various organic and inorganic polymers having low polarity and thermal stability have recently been proposed.

As organic polymers having a low dielectric constant, polyimide resins, polyarylene ether resins, aromatic hydrocarbon resins, and the like are known. Most of these organic polymers have a dielectric constant of 3.2 to 2.6, which has a low glass transition temperature, and thus, mechanical strength is significantly lower than that of SiO ₂ , and the coefficient of linear expansion is very high. Such organic polymers having low thermal stability, elastic modulus and high linear expansion coefficient may lower the reliability of the device or the wiring board.

In order to solve the thermal stability problem of the organic polymer as described above, the development of an organosilicate polymer using an alkoxy silane compound is in progress. The organosilicate polymer is prepared by the general method of hydrolyzing and condensing an alkoxy silane compound into an organic polymer having a constant molecular weight. Polymethylsilsesquioxane or polyhydrogensilsesquioxane, which is an alkoxy silane compound, has a relatively low dielectric constant of 3.0 or less and is thermally stable at 450 ° C. However, polysilsesquioxane is prone to cracking at a thickness of 1 μm or more due to shrinkage stress generated during the curing process, and has a problem that mechanical strength is not sufficient. In addition, since most of the alkoxysilane-based insulating materials currently used have a dielectric constant of 2.7 or more, it is a long-term goal to improve the mechanical properties while lowering the dielectric constant to 2.5 or less.

As a method of preparing an insulating film having a dielectric constant of 2.5 or less, a method of preparing a porous insulating film by producing an organic silicate of nanoparticles having a high molecular weight by hydrolysis and condensation reaction using a base catalyst and curing it is known. Publication 2001-354903)

In addition, in order to improve the mechanical strength of the porous insulating film, a coating composition for forming an insulating film in which an organosilicate polymer polymerized using an acid catalyst and an organosilicate polymer polymerized using a base catalyst is mixed.

However, when the low molecular weight acid catalyst reactant and the high molecular weight base catalyst reactant are mixed, the mechanical strength may be improved, but there is a problem in that the dielectric constant is sharply increased. Particularly, in the case of the base catalyst, the reactivity is very fast, so that the base catalyst was removed and an acid catalyst was added to stabilize the storage property. However, when an acid catalyst is added to the base catalyst reactant used in the hydrolysis condensation reaction, there is a possibility that salt may be formed, and foreign matter may occur during long-term storage. To this end, a small amount of water is added to the coating composition for forming the insulating film to increase the solubility of the foreign material salt so as to suppress the generation of foreign matters, but there is a problem in that the mechanical strength of the insulating film is not significantly improved while the storage property is improved.

As described above, various attempts have been made to produce an insulating film having low dielectric properties and excellent mechanical strength and elastic modulus. However, satisfactory results of simultaneously improving the insulation and mechanical strength of the low dielectric insulating film or the ultra-low dielectric porous insulating film for semiconductor devices have not been achieved. It is not enough until now.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a coating composition for forming an insulating film having a low dielectric constant, and at the same time improved mechanical strength (elastic modulus).

Another object of the present invention is to provide a method for producing a low dielectric insulating film of a semiconductor device capable of significantly improving low dielectric properties and mechanical strength.

It is still another object of the present invention to provide an insulating film of a semiconductor device in which low dielectric properties and mechanical strength are significantly improved.

Still another object of the present invention is to provide a semiconductor device including an insulating film excellent in low dielectric properties and mechanical strength.

1 is a graph measuring the molar ratio of hydroxy groups in a condensable functional group of the organopolysiloxane prepolymer prepared in Example 1 by ¹ H-NMR.

In order to achieve the above object, the present invention is a) an organopolysiloxane prepolymer having a weight average molecular weight of 500 to 30,000; It provides a coating composition for forming an insulating film comprising b) an organic solvent and c) water.

In another aspect, the present invention comprises the steps of: a) preparing an organopolysiloxane prepolymer having a weight average molecular weight of 500 to 30,000; b) mixing the i) prepared organic polysiloxane prepolymer, ii) an organic solvent, and iii) water to prepare a coating composition for forming an insulating film; c) applying the coating composition for forming an insulating film of step b) to the substrate of the semiconductor device; And d) drying and baking the coated coating composition for forming an insulating film of step c) to form an insulating film.

In another aspect, the present invention is a repeating unit prepared by the above method, the one or more silane compounds selected from the group consisting of silane compounds represented by the following formulas (1) to (3), the dimer or oligomer prepared therefrom hydrolyzed and condensation reaction The branch provides a low dielectric insulating film for semiconductor devices comprising an organopolysiloxane polymer.

[Formula 1]

Where

R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine,

R ² is straight or branched alkoxy having 1 to 4 carbon atoms,

p is an integer of 1 to 2,

[Formula 2]

Where

R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine,

R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms,

M is alkylene or phenylene having 1 to 6 carbon atoms,

q and r are each an integer of 0 to 2,

[Formula 3]

Where

R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine,

R ⁸ is hydrogen, hydroxy, or alkoxy having 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3.

R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine,

R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms,

m and n are each an integer of 3-7.

The present invention also provides a semiconductor device comprising an insulating film for a semiconductor device by the above method.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have been studying a composition for preparing an insulating film in which low dielectric properties and mechanical properties are simultaneously improved, using a specific low molecular weight organopolysiloxane prepolymer prepared in the presence of an acid catalyst and a composition containing a specific amount of water. When the insulating film is prepared, an insulating film having low dielectric properties and excellent mechanical strength can be obtained than when the insulating film is prepared using a composition containing no water or containing a small amount of water. When water is added, the mechanical strength is no longer improved, and the physical properties such as storage property and coating property are found to be lowered, thereby completing the present invention.

The low dielectric insulating film for semiconductor devices is prepared by applying a coating composition for forming an insulating film containing an organopolysiloxane prepolymer to a substrate and baking, and the silanol groups in the organic polysiloxane are condensation reaction during the baking process. Forms an O-Si bond. In this case, when water is present in the composition, the silanol functional group and the water form hydrogen bonds, and improve the intermolecular condensation during the bake process to form a network structure, the reaction rate is It can be faster, so that the crosslinking density can be further increased, and thus the mechanical strength can be improved.

The coating composition for forming an insulating film of the present invention includes an organopolysiloxane prepolymer, an organic solvent, and water having a weight average molecular weight of 500 to 30,000.

In order to effectively improve low dielectric properties and mechanical strength, the weight average molecular weight of the organopolysiloxane prepolymer is preferably 500 to 30,000, more preferably 500 to 10,000.

If the weight average molecular weight is less than 500, there is a fear that the coating property is lowered. In addition, when the weight average molecular weight of the organopolysiloxane prepolymer exceeds 30,000, the number of functional groups is significantly reduced, and the effect of increasing mechanical strength is insignificant. In addition, even when the organopolysiloxane prepolymer having a weight average molecular weight of 30,000 or less and the organopolysiloxane prepolymer having a weight average molecular weight of more than 30,000 are mixed, the low molecular weight organopolysiloxane prepolymer suppresses the formation of pores of the high molecular weight organopolysiloxane prepolymer. Dielectricity is difficult to implement.

Moreover, it is preferable that the molar ratio of the hydroxyl group with respect to the whole condensable functional group of the organopolysiloxane prepolymer is 80% or more, and it is more preferable that it is 90% or more. When the proportion of the hydroxy group is less than 80%, the number of functional groups that interact with water is small, and the crosslinking density is low, so that it is difficult to expect improvement in mechanical properties.

In addition, in the silane compound used for the preparation of the organopolysiloxane prepolymer, the mechanical properties of the insulating film on which a silane compound having a ratio of functional group / Si (non-hydrolysable functional groups per silicon atom) of 0.35 to 0.75 are finally produced. Preferred in terms of strength and insulation properties. When the functional group / Si ratio is less than 0.35, the mechanical strength is excellent but the low dielectric properties are bad, and when the ratio is more than 0.75, the condensation-reactive functional group may be small, so that the mechanical strength improvement may be insignificant, and the crosslinking density is low. The strength is not good.

As the organopolysiloxane prepolymer, any organic polysiloxane prepolymer including silicon, oxygen, carbon, and hydrogen may be used. Preferably, the organopolysiloxane prepolymer may be selected from the group consisting of silane compounds represented by the following Chemical Formulas 1 to 3 in the molecule: One or more silane compounds, dimers or oligomers produced therefrom, may be used that contain repeating units hydrolyzed and condensed.

[Formula 1]

Where

R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine,

R ² is straight or branched alkoxy having 1 to 4 carbon atoms,

p is an integer of 1 to 2,

[Formula 2]

Where

R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine,

R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms,

M is alkylene or phenylene having 1 to 6 carbon atoms,

q and r are each an integer of 0 to 2,

[Formula 3]

Where

R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine,

R ⁸ is hydrogen, hydroxy, or alkoxy having 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3;

R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine,

R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms,

m and n are each an integer of 3-7.

The organic solvent used in the coating composition for forming an insulating film of the present invention can be used as long as it does not adversely affect the coating property of the insulating film, but it is preferable to use an ether solvent or an ester solvent.

Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Ether solvents such as glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, or propylene glycol dipropyl ether; Diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate, propylene Ester solvent, such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol diacetate, or propylene glycol diacetate, etc. can be used 1 type, or 2 or more types.

Among the above solvents, it is more preferable to use a non-alcohol ether solvent or a non-alcohol ester solvent which does not contain a hydroxyl group at the terminal, in view of mechanical strength.

The organic solvent is preferably included in an amount of 200 to 2,000 parts by weight based on 100 parts by weight of the organopolysiloxane prepolymer. When the content of the organic solvent is less than 200 parts by weight, the coating property may deteriorate and the storage safety of the insulating film may be deteriorated. When the content of the organic solvent exceeds 2,000 parts by weight, an insulating film having a sufficient thickness may not be obtained.

Water used in the coating composition for forming an insulating film of the present invention is used as a hydrolysis of the silane compound, but is included in a specific content in the final coating composition. It is preferably included 4 to 60 parts by weight, more preferably 10 to 40 parts by weight based on 100 parts by weight of the organopolysiloxane prepolymer. When the content of water is less than 4 parts by weight, the improvement in mechanical strength and low dielectric properties is insignificant, and when the content of water exceeds 60 parts by weight, the mechanical strength is not further improved. On the other hand, due to compatibility with the coating solvent may reduce the coating property, the storage stability of the solution may be worse.

The coating composition for forming an insulating film of the present invention may further include a pore forming material for uniformly distributing pores of a predetermined size in the insulating film in order to manufacture an insulating film having a dielectric constant of 2.5 or less.

The pore-forming material may be used as long as it is compatible with the organopolysiloxane prepolymer and the organic solvent and can be thermally decomposed at 200 to 450 ° C. Preferably, linear organic molecules or polymers and cross-linked organic compounds are used. A molecule or a polymer, a hyper-branched organic molecule or a polymer, or a dendrimer organic molecule or a polymer may be used.

Preferred examples of the pore-forming material include aliphatic ethers or polyethers having 2 to 12 carbon atoms of repeating units, aliphatic esters or polyesters, aliphatic carbonates or polycarbonates, and aliphatic acrylates or polyacrylates. The molecular weight of the pore-forming material is preferably in the range of 500 to 100,000, more preferably in the range of 500 to 50,000 in terms of the polystyrene equivalent weight average molecular weight.

In addition, the pore forming material may contain a silane compound in the molecule to improve compatibility with the organopolysiloxane prepolymer, and the pore forming material containing the silane compound may be added and copolymerized when preparing the organopolysiloxane prepolymer. It may be.

The pore-forming material is preferably included in 100 parts by weight or less, more preferably 5 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane prepolymer. When the content of the pore-forming material exceeds 100 parts by weight, the mechanical strength of the insulating film is lowered.

The insulating film forming coating composition is prepared by preparing an organopolysiloxane prepolymer having a weight average molecular weight of 500 to 30,000, and mixing the prepared organopolysiloxane prepolymer with an organic solvent and water.

At this time, the organopolysiloxane prepolymer may be prepared by mixing a silane compound with an acid catalyst and a mixture of water or an organic solvent, and hydrolyzing and condensation reaction under acidic conditions of pH 4 or less, preferably pH 1 to 4. have.

The silane compound used for the polymerization may be any silane compound containing silicon, oxygen, carbon and hydrogen, preferably at least one silane compound selected from the silane compounds represented by the above formulas (1) to (3), Dimers or oligomers prepared therefrom can be used.

In addition, the acid catalyst used in the preparation of the organopolysiloxane prepolymer serves to promote hydrolysis and condensation of the silane compound. Examples of the acid catalyst are not particularly limited, and preferred examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, Trifluoroacetic acid, oxalic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid, p-aminobenzoic acid, or p-toluenesulfonic acid. The said catalyst can use 1 type (s) or 2 or more types simultaneously or stepwise.

The addition amount of the catalyst can be adjusted according to the reaction conditions, preferably used less than 2 moles per mole of the silane compound used in the preparation of the organopolysiloxane prepolymer, more preferably 0.000001 to 2 moles are used. Do. When the amount of the catalyst exceeds 2 mol per mol of the silane compound, even at low concentrations, the reaction rate is very fast, making it difficult to control the molecular weight and easily causing gel.

The organopolysiloxane prepolymer may be prepared by reacting in the presence of water and an organic solvent, or by reacting in bulk in the presence of water without an organic solvent, or may be prepared by performing the two reactions stepwise.

At this time, the amount of water to be used is preferably contained in 3 to 40 moles with respect to 1 mole of the silane compound. If the amount of water is less than 3 moles, the hydrolysis reaction of the functional groups does not occur sufficiently, which adversely affects the physical properties. If the content is more than 40 moles, the reaction solution is uneven.

The organic solvent used in the preparation of the organopolysiloxane prepolymer is not particularly limited as long as it does not cause great trouble in the hydrolysis and condensation reaction of the silane compound or the silane oligomer. Preferably, aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, 2,2,4-trimethylpentane, cyclohexane, or methylcyclo hexane; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, xylene, trimethyl benzene, ethyl benzene, or methyl ethyl benzene; Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, diethyl ketone, cyclohexanone, methylcyclohexanone, or acetylacetone; Tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl ether, n-propyl ether, i-propyl ether, n-butyl ether, diglyme, dioxin, dimethyldioxine, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl Ether solvents such as ether or propylene glycol dipropyl ether; Diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate, propylene Ester solvents such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol diacetate, or propylene glycol diacetate; Or N-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N-ethylacetide Amide solvents such as amide, N, N-dimethylacetamide, or N, N-diethylacetamide can be used. The said organic solvent can be used 1 type or in mixture of 2 or more types.

Although the reaction temperature of the hydrolysis and condensation reaction in the preparation of the organopolysiloxane prepolymer is not particularly limited, it is preferable to react at a temperature of 0 to 100 ℃. The reaction temperature may be maintained at a constant temperature during the reaction, or may be reacted while controlling the temperature intermittently or continuously.

In the reaction process, a lower alcohol, which is a reaction byproduct, is generated. The lower alcohol may lower the coating property and the mechanical properties of the insulating film. In addition, even when the alcohol solvent having a high boiling point (boiling point) is included in addition to the lower alcohol, which is a reaction by-product, the functional group of the organopolysiloxane prepolymer is capable of substitution reaction, which is not preferable in terms of mechanical properties. desirable.

The organopolysiloxane prepolymer prepared by the above method is a repeating unit in which at least one silane compound selected from the group consisting of silane compounds represented by Formulas 1 to 3 in the molecule, a dimer or oligomer prepared therefrom is hydrolyzed and condensed. It includes, it is preferable that the weight average molecular weight is 500 to 30,000.

In order to manufacture the coating composition for forming an insulating film of the present invention comprising the organopolysiloxane prepolymer, the organic solvent used in the preparation of the organic polysiloxane prepolymer may be used as an organic solvent of the coating composition for forming an insulating film as it is, the organic The specific organic solvent may be removed from the organic solvent used in the preparation of the polysiloxane prepolymer, and a new solvent may be added. The organic solvent used in the preparation of the organic polysiloxane prepolymer may be removed, and the organic solvent having excellent coating property may be added. It can also be used.

Preferable examples of the organic solvent having excellent coating properties include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol. Ether solvents such as monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, or propylene glycol dipropyl ether; Diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate, propylene Ester solvents such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol diacetate, or propylene glycol diacetate; and the like, and one or two or more mixed solvents may be used.

In addition, it is more preferable in terms of mechanical strength to use a non-alcohol ether solvent or a non-alcohol ester solvent which does not contain a hydroxy group at the end of the solvent.

The coating composition for forming an insulating film prepared by the above method preferably includes i) 200 to 2000 parts by weight of the organic solvent and iii) 4 to 60 parts by weight of water based on 100 parts by weight of the organopolysiloxane prepolymer.

In addition, the composition may further include a pore-forming material to prepare an insulating film having a dielectric constant of 2.5 or less.

The pore-forming material may be used as long as it is compatible with the organopolysiloxane prepolymer and the organic solvent and can be thermally decomposed at 200 to 450 ° C. Preferably, linear organic molecules or polymers and cross-linked organic compounds are used. A molecule or a polymer, a hyper-branched organic molecule or a polymer, or a dendrimer organic molecule or a polymer may be used.

The present invention provides a low dielectric insulating film of a semiconductor device manufactured by applying a coating composition for forming an insulating film including the above components to a substrate, followed by drying and baking.

The substrate may be a silicon wafer, a SiO ₂ wafer, a SiN wafer, a compound semiconductor, or the like.

As a method of applying the coating composition for forming an insulating film, a conventional coating method may be used, and preferably, a film having a predetermined thickness may be formed by spin coating, dipping, roll coating, spraying, or the like. Preferably, when manufacturing a multilayer circuit interlayer insulating film of a semiconductor device, it is preferable to use a spin coat method.

The insulating film may control the film thickness by changing the viscosity of the coating composition and the rotational speed of the spin coater. In general, when the insulating film is used as an interlayer insulating film of a multilayer circuit structure of a semiconductor device, the thickness of the insulating film is 0.05 to 2 μm. It is suitable.

After the insulating film is coated with the coating composition, a low dielectric insulating film having a three-dimensional structure may be formed through a drying process and a baking (curing) process. The drying process may be performed by conventional methods, and may include a pre-bake process and a soft-bake process. During the prebaking step, the used organic solvent is gradually evaporated, during the softbaking step, a certain amount of the functional group is crosslinked, and the remaining functional group is further reacted during the subsequent baking step.

The drying step is preferably carried out at a temperature of 50 to 250 ℃. When drying temperature is less than 50 degreeC, sufficient drying does not arise, and when it exceeds 250 degreeC, hardening may advance in the state which is not fully dried, and it cannot form a uniform insulating film.

Moreover, it is preferable to perform the said baking process at the temperature of at least 300 degreeC, and it is more preferable to carry out at the temperature of 300-500 degreeC. When the firing temperature is less than 300 ° C., condensation polymerization of the residual functional groups of the organic polysiloxane polymer does not occur completely, and thus the strength of the insulating film is lowered, and the dielectric properties may be lowered due to the presence of the residual functional groups. In addition, the upper limit of the firing temperature can be appropriately adjusted according to the thermal stability of the low dielectric insulating film of the present invention and the semiconductor device manufactured using the same.

The drying step and the firing step may be carried out while continuously increasing the temperature at a constant rate, or may be carried out intermittently. When intermittently, it is preferable to perform the drying process and the firing process for 1 minute to 5 hours, respectively. In this case, the heating method may be a hot plate, an oven, a furnace, or the like, and the heating atmosphere may be an inert gas atmosphere such as nitrogen, argon or helium, an oxygen atmosphere such as an oxygen-containing gas (for example, air, etc.), a vacuum state, or A gas atmosphere containing ammonia and hydrogen can be used. The heating method may be performed by the same heating method as the drying step and the firing step, or may be performed by different methods.

In addition, the present invention provides an insulating film manufactured as described above and a semiconductor device including the insulating film. Since the insulating film obtained as described above has excellent insulating property and excellent mechanical strength, the high density integrated circuit (LSI: Large scale integration, system high density integrated circuit (LSI), interlayer insulating film for semiconductor devices such as DRAM, SDRAM, RDRAM, D-RDRAM, semiconductor device interlayer capping layer, hard mask layer, etch Good for use as an etch stop layer. In addition, it can be used as a protective film and an insulating film of various uses, for example, a protective film such as a semiconductor device surface coating film, an interlayer insulating film of a multilayer wiring substrate, a protective film for a liquid crystal display device, an insulation prevention film and the like.

The coating composition for forming an insulating film according to the present invention, the insulating film of a semiconductor device to which the composition is applied and cured, and a semiconductor device including the insulating film have an effect of remarkably improving low dielectric properties and mechanical strength.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Manufacture of Coating Composition for Insulating Film Formation)

100.0 g of methyltrimethoxy silane and 111.75 g of tetramethoxy silane were added to 490 g of an organic solvent, tetrahydrofuran, and then 185 g of a nitric acid aqueous solution having a concentration of 0.01 N was slowly added. After reacting this at room temperature for 30 minutes, the temperature was gradually raised and heated and refluxed for about 16 hours. After completion of the reaction, the reaction solution was diluted with diethyl ether solvent and washed with water until the pH was neutral. Magnesium sulfate was added to the obtained organic layer to completely remove the remaining water, and the solvent of the remaining organic layer was completely removed in a vacuum oven to obtain an organopolysiloxane prepolymer. The weight average molecular weight of the organopolysiloxane prepolymer obtained at this time was 2,500. The molar ratio of the hydroxy group in the condensable functional group of the organopolysiloxane prepolymer thus obtained is 90%. The organopolysiloxane prepolymer was dissolved in a 20% by weight solution in propylene glycol methyl ether acetate solvent to prepare a coating composition for forming an insulating film.

(Manufacture of insulating film)

1.0 g of water was added to the prepared coating composition for forming an insulating film, followed by spin coating on a silicon wafer to obtain a thin film, and prebaked at a temperature of 80 ° C. and 150 ° C. for 1 minute on a hot plate, followed by a furnace. At 430 ° C. and then cured for 1 hour to form an insulating film.

The dielectric constant of the prepared insulating film is 2.98, the modulus of elasticity (Modulus) is 16.2 GPa, the hardness (Hardness) is 2.45 GPa.

Example 2

(Manufacture of Coating Composition for Insulating Film Formation)

In the same manner as in Example 1 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

20 g of the coating composition for forming the insulating film, a polyethylene oxide (PEO) -polypropylene oxide (PPO) -polyethylene oxide (PEO) triblock air containing 1.0 g of water, a molecular weight of 5,000, and 30% by weight of polyethylene oxide (PEO) An insulating film was prepared in the same manner as in Example 1, except that 8.6 g of a solution in which a triblock copolymer was dissolved in propylene glycol methyl ether acetate at 20 wt% was added.

The dielectric constant of the prepared insulating film was 2.26, the modulus of elasticity was 5.6 Gpa, and the hardness was 0.72 GPa.

Comparative Example 1

(Manufacture of Coating Composition for Insulating Film Formation)

In the same manner as in Example 1 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1 except that water was not added.

The dielectric constant of the prepared insulating film was 3.16, the modulus of elasticity was 14.6 GPa, and the hardness was 2.1 GPa.

Comparative Example 2

(Manufacture of Coating Composition for Insulating Film Formation)

In the same manner as in Example 1 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1, except that 0.05 g of water was added.

The dielectric constant of the prepared insulating film was 3.14, the modulus of elasticity was 14.4 GPa, and the hardness was 2.09 GPa.

Comparative Example 3

(Manufacture of Coating Composition for Insulating Film Formation)

100.0 g of methyltrimethoxy silane and 111.75 g of tetramethoxy silane were added to 490 g of an organic solvent, tetrahydrofuran, and then 46.0 g of a nitric acid aqueous solution having a concentration of 0.01 N was slowly added. After reacting this at room temperature for 30 minutes, the temperature was gradually raised and heated and refluxed for about 16 hours. After completion of the reaction, the reaction solution was diluted with diethyl ether solvent and washed with water until the pH was neutral. Magnesium sulfate was added to the obtained organic layer to completely remove the remaining water, and the solvent of the remaining organic layer was completely removed in a vacuum oven to obtain an organopolysiloxane prepolymer. The weight average molecular weight of the organopolysiloxane prepolymer obtained at this time was 3,300. The molar ratio of the hydroxyl group in the condensable functional group of the organopolysiloxane prepolymer thus obtained is 60%. The organopolysiloxane prepolymer was dissolved in a 20% by weight solution in propylene glycol methyl ether acetate solvent to prepare a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1, except that 0.5 g of water was added.

The dielectric constant of the prepared insulating film was 3.10, the modulus of elasticity was 12.4 GPa, and the hardness was 1.83 GPa.

Comparative Example 4

(Manufacture of Coating Composition for Insulating Film Formation)

In the same manner as in Example 1 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 2, except that water was not added.

The dielectric constant of the prepared insulating film was 2.33, the modulus of elasticity was 4.9 GPa, and the hardness was 0.60 GPa.

Comparative Example 5

(Manufacture of Coating Composition for Insulating Film Formation)

7.5 g of methyltrimethoxysilane and 11.46 g of tetraethoxysilane were added to a mixed solution of 104.1 g of distilled water and 266.4 g of ethanol, and then 3.0 g of 40% methylamine aqueous solution was added thereto and reacted at 60 ° C. for 2 hours. 120 g of glycol monopropyl ether were added and the solvent was evaporated using a rotary evaporator until the total weight of the solution was 60 g. At this time, the weight average molecular weight of the prepared organopolysiloxane prepolymer was 890,000.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1, except that 1.0 g of water was added to 20 g of the coating composition for forming an insulating film.

The dielectric constant of the prepared insulating film was 2.21, the modulus of elasticity was 4.41 GPa, and the hardness was 0.60 GPa.

Comparative Example 6

(Manufacture of Coating Composition for Insulating Film Formation)

In the same manner as in Comparative Example 5 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1 except that water was not added.

The dielectric constant of the prepared insulating film was 2.20, the modulus of elasticity was 4.31 GPa, and the hardness was 0.59 GPa.

Comparative Example 7

(Preparation of Coating Composition I for Insulating Film Formation (Base Catalyst Reaction))

In the same manner as in Comparative Example 5 was prepared a coating composition for forming an insulating film.

(Manufacture of Coating Composition II for Insulating Film Formation (Acid Catalyst))

100.0 g of methyltrimethoxy silane and 44.7 g of tetramethoxy silane were added to 300 g of an organic solvent, tetrahydrofuran. Then, 262.2 g of distilled water was further mixed, and 29.1 g of an aqueous solution of nitric acid having a concentration of 0.1 N was slowly added. After reacting this at room temperature for 30 minutes, the temperature was gradually raised and heated and refluxed overnight (about 24 hours). After completion of the reaction, the reaction solution was diluted with diethyl ether solvent and washed with water until the pH was neutral. Magnesium sulfate was added to the obtained organic layer to completely remove the remaining water, and the solvent of the remaining organic layer was completely removed in a vacuum oven to obtain an organopolysiloxane prepolymer. At this time, the weight average molecular weight of the obtained organopolysiloxane prepolymer was 1,680. The organopolysiloxane prepolymer was dissolved in a 20% by weight solution in propylene glycol methyl ether acetate solvent to prepare a coating composition for forming an insulating film.

(Manufacture of insulating film)

An insulating film was prepared in the same manner as in Example 1, except that 3.0 g of water was added to a solution obtained by mixing 60 g of the coating composition I for forming the insulating film and 20 g of the coating composition II for forming the insulating film.

The dielectric constant of the prepared insulating film was 2.49, the modulus of elasticity was 6.8 GPa, and the hardness was 1.0 GPa.

Comparative Example 8

(Preparation of Coating Composition I for Insulating Film Formation (Base Catalyst Reaction))

In the same manner as in Comparative Example 5 was prepared a coating composition for forming an insulating film.

(Manufacture of Coating Composition II for Insulating Film Formation (Acid Catalyst))

A coating composition for forming an insulating film was prepared in the same manner as in Comparative Example 7.

(Manufacture of insulating film)

An insulating film was manufactured in the same manner as in Comparative Example 7, except that water was not added.

The dielectric constant of the prepared insulating film was 2.48, the modulus of elasticity was 6.7 GPa, and the hardness was 1.0 GPa.

Comparative Example 9

(Preparation of Coating Composition I for Insulating Film Formation (Base Catalyst Reaction))

In the same manner as in Comparative Example 5 was prepared a coating composition for forming an insulating film.

(Manufacture of insulating film)

A polyethylene oxide (PEO) -polypropylene oxide (PPO) -polyethylene oxide (PEO) triblock copolymer having a molecular weight of 5,000 and containing 30% by weight of polyethylene oxide (PEO) in 20 g of the coating composition for forming an insulating film An insulating film was prepared in the same manner as in Example 1 except that 0.3 g was added.

The dielectric constant of the prepared insulating film was 2.33, the modulus of elasticity was 4.8 GPa, and the hardness was 0.56.

The mechanical strength and dielectric constant of the insulating films prepared in Examples 1 and 2 and Comparative Examples 1 to 9 were measured by the following method, and the results are shown in Table 1 below.

A) Mechanical strength-After the insulating film was cured by spin coating on the silicon wafer, it was measured using a nanoindenter.

B) Dielectric constant-After curing by coating an insulating film on a silicon wafer by a metal insulator semiconductor (MIS) method by spin coating, A1 was deposited on the insulating film and then measured at 1 MHz.

C) The molar ratio of the hydroxyl group in the condensable functional group of the organopolysiloxane prepolymer prepared in Example 1 was measured by ¹ H-NMR, and the result is shown in FIG. 1.

Weight average molecular weight Water (g) Pore-forming substance permittivity Modulus of elasticity (GPa) Longitude (GPa) Example 1 2,500 1.0 X 2.98 16.2 2.45 Example 2 2,500 1.0 O 2.26 5.6 0.72 Comparative Example 1 2,500 X X 3.16 14.6 2.10 Comparative Example 2 2,500 0.05 X 3.14 14.4 2.09 Comparative Example 3 3,300 0.5 X 3.10 12.8 1.83 Comparative Example 4 2,500 X O 2.33 4.9 0.60 Comparative Example 5 890,000 1.0 X 2.21 4.4 0.6 Comparative Example 6 890,000 X X 2.20 4.31 0.59 Comparative Example 7 890,000+ 1680 3.0 X 2.49 6.8 1.0 Comparative Example 8 890,000+ 1680 X X 2.48 6.7 1.0 Comparative Example 9 890,000 1.0 O 2.33 4.8 0.56

As shown in Table 1 above, when comparing the insulating film prepared by Examples 1 and 2 with the insulating film prepared by Comparative Examples 1 to 4, a specific low molecular weight organopolysiloxane prepolymer and a specific amount of water It can be seen that the insulating film of Example 1 prepared from the coating composition for forming an insulating film has a lower dielectric constant and a higher elastic modulus than the insulating films of Comparative Examples 1 to 4 containing no water or containing a small amount of water.

In addition, in the insulating films of Example 2 and Comparative Example 4 in which pores were added to form pores, the insulating films of Example 2 containing water showed low dielectric constant and high elastic modulus.

On the other hand, in the case of containing high molecular weight organic polysiloxane by base reaction as shown in Comparative Examples 5 to 9, the improvement of dielectric properties and strength by water during the drying and curing process is insignificant, and also in Comparative Examples 5 and 9 As shown, when the high molecular weight organopolysiloxane prepolymer is included, the dielectric constant can be effectively lowered, but a small amount of the low molecular weight organopolysiloxane suppresses pore formation, thereby increasing the dielectric constant.

In addition, in the case of Comparative Example 9 using a high molecular weight organopolysiloxane prepolymer and a pore-forming material, pore formation was not effective, but rather a dielectric constant was increased.

Through Table 1, it can be seen that an insulating film having excellent dielectric strength while having a low dielectric constant from the coating composition for forming an insulating film of the present invention.

According to the present invention, it is possible to manufacture a coating composition for forming an insulating film, which has significantly improved low dielectric properties and mechanical strength at the same time, an insulating film of a semiconductor device to which the composition is applied and cured, and a semiconductor device including the insulating film.

Claims (18)

a) organopolysiloxane prepolymer having a weight average molecular weight of 500 to 30,000; b) organic solvents and c) water Coating composition for forming an insulating film comprising a. The method of claim 1, wherein the composition a) 100 parts by weight of the organopolysiloxane prepolymer b) 200 to 2000 parts by weight of the organic solvent; And c) 5 to 60 parts by weight of water Coating composition for insulating film formation comprising a. The coating composition of claim 1, wherein the organopolysiloxane prepolymer has a molar ratio of at least 80% of a hydroxyl group relative to the entire condensable functional group of the epsipolysiloxane prepolymer. The coating composition of claim 1, wherein the organopolysiloxane prepolymer has a ratio of functional groups (Si / Si) that is not hydrolyzable to silicon atoms. The coating composition of claim 1, wherein the organic solvent is a non-alcohol ether solvent or a non-alcohol ester solvent. According to claim 1, wherein the organopolysiloxane prepolymer is a hydrolysis and condensation reaction of at least one silane compound selected from the group consisting of silane compounds represented by the following formulas (1) to (3), a dimer or oligomer prepared therefrom Coating composition for forming an insulating film comprising a repeating unit. [Formula 1] Where R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine, R ² is straight or branched alkoxy having 1 to 4 carbon atoms, p is an integer of 1 to 2, [Formula 2] Where R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine, R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms, M is alkylene or phenylene having 1 to 6 carbon atoms, q and r are each an integer of 0 to 2, [Formula 3] Where R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ⁸ is hydrogen, hydroxy, or alkoxy having 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3; R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms, m and n are each an integer of 3-7. The coating composition of claim 1, wherein the composition further comprises d) a pore forming material. The coating composition of claim 7, wherein the composition further comprises d) a pore-forming material in an amount of 5 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane prepolymer. The method of claim 7, wherein the pore-forming material is linear organic molecules, linear organic polymers, cross-linked organic molecules, cross-linked organic polymers, hyper-branched organic polymers pyrolyzed at 200 to 450 ℃ A coating composition for forming an insulating film, which is one or more materials selected from the group consisting of molecules, hyperbranched polymers, dendrimer organic molecules, and dendrimer organic polymers. a) preparing an organopolysiloxane prepolymer having a weight average molecular weight of 500 to 30,000; b) mixing the i) prepared organic polysiloxane prepolymer, ii) an organic solvent, and iii) water to prepare a coating composition for forming an insulating film; c) applying the coating composition for forming an insulating film of step b) to the substrate of the semiconductor device; And d) drying and baking the coated coating composition for forming an insulating film of step c) to form an insulating film Method for producing a low dielectric insulating film comprising a. The method of claim 10, wherein the organopolysiloxane prepolymer of step a) i) at least one silane compound selected from the group consisting of silane compounds represented by the following Chemical Formulas 1 to 3, dimers or oligomers prepared therefrom; ii) acid catalysts; And iii) water or a mixture of water and organic solvent A method of producing a low dielectric insulating film which is prepared by mixing, hydrolysis and condensation reaction. [Formula 1] Where R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine, R ² is straight or branched alkoxy having 1 to 4 carbon atoms, p is an integer of 1 to 2, [Formula 2] Where R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine, R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms, M is alkylene or phenylene having 1 to 6 carbon atoms, q and r are each an integer of 0 to 2, [Formula 3] Where R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ⁸ is hydrogen, hydroxy, or alkoxy having 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3; R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms, m and n are each an integer of 3-7. The method of claim 10, wherein the organopolysiloxane prepolymer of step a) comprises at least one silane compound selected from the group consisting of silane compounds represented by the following Chemical Formulas 1 to 3 in a molecule thereof, and a dimer or oligomer prepared therefrom is hydrolyzed. And a condensation reaction repeating unit. [Formula 1] Where R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine, R ² is straight or branched alkoxy having 1 to 4 carbon atoms, p is an integer of 1 to 2, [Formula 2] Where R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine, R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms, M is alkylene or phenylene having 1 to 6 carbon atoms, q and r are each an integer of 0 to 2, [Formula 3] Where R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ⁸ is hydrogen, hydroxy, or alkoxy having 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3; R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms, m and n are each an integer of 3-7. The method of claim 10, wherein the composition of step b) comprises: i) 100 parts by weight of an organopolysiloxane prepolymer, based on the total weight; ii) 200 to 2000 parts by weight of the organic solvent and iii) 4 to 60 parts by weight of water. The method of claim 10, wherein the composition of step b) further comprises iv) a pore forming material. 15. The method of claim 14, wherein the composition further comprises 5 to 100 parts by weight of a pore-forming material based on 100 parts by weight of the organopolysiloxane prepolymer. 15. The method of claim 14, wherein the pore-forming material is linear organic molecules, linear organic polymers, cross-linked organic molecules, cross-linked organic polymers, hyper-branched organic polymers pyrolyzed at 200 to 450 ℃ A method for producing a low dielectric insulating film which is at least one material selected from the group consisting of molecules, hyperbranched polymers, dendrimer organic molecules, and dendrimer organic polymers. A repeating unit prepared by the method according to claim 10, wherein at least one silane compound selected from the group consisting of silane compounds represented by the following Chemical Formulas 1 to 3, and a dimer or oligomer prepared therefrom is hydrolyzed and condensed: A low dielectric insulating film for semiconductor devices comprising an organopolysiloxane polymer having. [Formula 1] Where R ¹ is straight or branched alkyl of 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine, R ² is straight or branched alkoxy having 1 to 4 carbon atoms, p is an integer of 1 to 2, [Formula 2] Where R ³ , and R ⁵ are each independently hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, unsubstituted or substituted with fluorine, R ⁴ and R ⁶ are each independently straight or branched alkoxy having 1 to 4 carbon atoms, M is alkylene or phenylene having 1 to 6 carbon atoms, q and r are each an integer of 0 to 2, [Formula 3] Where R ⁷ is hydrogen, fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ⁸ is hydrogen, hydroxy, or alkoxy of 1 to 4 carbon atoms on straight or branched chain, or — (CH ₂ ) a-SiR ⁹ R ¹⁰ , wherein a is 2 or 3, R ⁹ is fluorine, aryl, vinyl, allyl, linear or branched alkyl having 1 to 4 carbon atoms, optionally substituted with fluorine, R ¹⁰ is straight or branched alkoxy having 1 to 4 carbon atoms, m and n are each an integer of 3-7. A semiconductor device comprising the low dielectric insulating film for semiconductor device according to claim 17.